On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study

Autores
Fagioli, Ulises; Garcia Einschlag, Fernando Sebastian; Cobos, Carlos Jorge; Ruiz, Gustavo Teodosio; Feliz, Mario Ruben; Wolcan, Ezequiel
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We have studied the reaction between pz-CO2-Re(CO)3(bpy) and perchloric acid in acetonitrile by following the UV-vis and IR spectral changes in the reaction mixture. A fast equilibrium was found to be established between solvated protons, pz-CO2-Re(CO)3(bpy) and the protonated intermediate [pz-C(OH)O-Re(CO)3(bpy)]+ which finally yields pz-COOH and Re(CO)3(bpy)(CH3CN)+ as reaction products. This intermediate has been characterized by UV-vis and IR spectroscopies and by DFT calculations. The fully optimized DFT/CPCM structures for pz-CO2-Re(CO)3(bpy) and [pz-C(OH)O-Re(CO)3(bpy)]+ were compared with the X-ray structure of pz-CO2- Re(CO)3(bpy). The structural parameters associated to the carboxyl group in the protonated intermediate are between those of pz-CO2-Re(CO)3(bpy) and pz-COOH. Multivariate curve resolution methods were employed to obtain the spectrum of the protonated intermediate and the concentration profiles from the full matrix of timeresolved UV-vis spectra. The proposed mechanism was numerically simulated by using Runge-Kutta methods. Model parameters were estimated by non-linear regression fitting of the concentration profiles, yielding values of log(K) = 4.9 ± 0.3 and k = 0.16 ± 0.03 min-1 for the formation equilibrium constant and the decay rate constant of the protonated intermediate, respectively.
Fil: Fagioli, Ulises. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Garcia Einschlag, Fernando Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Feliz, Mario Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
Re-carboxylate
pyrazinic
non-linear regression
Runge-Kutta
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/278677
Acceder
id CONICETDig_3081403e2962f0978f7b1e16a2d6969a
oai_identifier_str oai:ri.conicet.gov.ar:11336/278677
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic StudyFagioli, UlisesGarcia Einschlag, Fernando SebastianCobos, Carlos JorgeRuiz, Gustavo TeodosioFeliz, Mario RubenWolcan, EzequielRe-carboxylatepyrazinicnon-linear regressionRunge-Kuttahttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We have studied the reaction between pz-CO2-Re(CO)3(bpy) and perchloric acid in acetonitrile by following the UV-vis and IR spectral changes in the reaction mixture. A fast equilibrium was found to be established between solvated protons, pz-CO2-Re(CO)3(bpy) and the protonated intermediate [pz-C(OH)O-Re(CO)3(bpy)]+ which finally yields pz-COOH and Re(CO)3(bpy)(CH3CN)+ as reaction products. This intermediate has been characterized by UV-vis and IR spectroscopies and by DFT calculations. The fully optimized DFT/CPCM structures for pz-CO2-Re(CO)3(bpy) and [pz-C(OH)O-Re(CO)3(bpy)]+ were compared with the X-ray structure of pz-CO2- Re(CO)3(bpy). The structural parameters associated to the carboxyl group in the protonated intermediate are between those of pz-CO2-Re(CO)3(bpy) and pz-COOH. Multivariate curve resolution methods were employed to obtain the spectrum of the protonated intermediate and the concentration profiles from the full matrix of timeresolved UV-vis spectra. The proposed mechanism was numerically simulated by using Runge-Kutta methods. Model parameters were estimated by non-linear regression fitting of the concentration profiles, yielding values of log(K) = 4.9 ± 0.3 and k = 0.16 ± 0.03 min-1 for the formation equilibrium constant and the decay rate constant of the protonated intermediate, respectively.Fil: Fagioli, Ulises. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Garcia Einschlag, Fernando Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Feliz, Mario Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaAmerican Chemical Society2011-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/278677Fagioli, Ulises; Garcia Einschlag, Fernando Sebastian; Cobos, Carlos Jorge; Ruiz, Gustavo Teodosio; Feliz, Mario Ruben; et al.; On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study; American Chemical Society; Journal of Physical Chemistry A; 115; 40; 8-2011; 10979-109871089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/pdfplus/10.1021/jp206328qinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp206328qinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-01-14T11:50:09Zoai:ri.conicet.gov.ar:11336/278677instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982026-01-14 11:50:09.556CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study
title On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study
spellingShingle On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study
Fagioli, Ulises
Re-carboxylate
pyrazinic
non-linear regression
Runge-Kutta
title_short On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study
title_full On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study
title_fullStr On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study
title_full_unstemmed On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study
title_sort On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study
dc.creator.none.fl_str_mv Fagioli, Ulises
Garcia Einschlag, Fernando Sebastian
Cobos, Carlos Jorge
Ruiz, Gustavo Teodosio
Feliz, Mario Ruben
Wolcan, Ezequiel
author Fagioli, Ulises
author_facet Fagioli, Ulises
Garcia Einschlag, Fernando Sebastian
Cobos, Carlos Jorge
Ruiz, Gustavo Teodosio
Feliz, Mario Ruben
Wolcan, Ezequiel
author_role author
author2 Garcia Einschlag, Fernando Sebastian
Cobos, Carlos Jorge
Ruiz, Gustavo Teodosio
Feliz, Mario Ruben
Wolcan, Ezequiel
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Re-carboxylate
pyrazinic
non-linear regression
Runge-Kutta
topic Re-carboxylate
pyrazinic
non-linear regression
Runge-Kutta
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We have studied the reaction between pz-CO2-Re(CO)3(bpy) and perchloric acid in acetonitrile by following the UV-vis and IR spectral changes in the reaction mixture. A fast equilibrium was found to be established between solvated protons, pz-CO2-Re(CO)3(bpy) and the protonated intermediate [pz-C(OH)O-Re(CO)3(bpy)]+ which finally yields pz-COOH and Re(CO)3(bpy)(CH3CN)+ as reaction products. This intermediate has been characterized by UV-vis and IR spectroscopies and by DFT calculations. The fully optimized DFT/CPCM structures for pz-CO2-Re(CO)3(bpy) and [pz-C(OH)O-Re(CO)3(bpy)]+ were compared with the X-ray structure of pz-CO2- Re(CO)3(bpy). The structural parameters associated to the carboxyl group in the protonated intermediate are between those of pz-CO2-Re(CO)3(bpy) and pz-COOH. Multivariate curve resolution methods were employed to obtain the spectrum of the protonated intermediate and the concentration profiles from the full matrix of timeresolved UV-vis spectra. The proposed mechanism was numerically simulated by using Runge-Kutta methods. Model parameters were estimated by non-linear regression fitting of the concentration profiles, yielding values of log(K) = 4.9 ± 0.3 and k = 0.16 ± 0.03 min-1 for the formation equilibrium constant and the decay rate constant of the protonated intermediate, respectively.
Fil: Fagioli, Ulises. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Garcia Einschlag, Fernando Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Feliz, Mario Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description We have studied the reaction between pz-CO2-Re(CO)3(bpy) and perchloric acid in acetonitrile by following the UV-vis and IR spectral changes in the reaction mixture. A fast equilibrium was found to be established between solvated protons, pz-CO2-Re(CO)3(bpy) and the protonated intermediate [pz-C(OH)O-Re(CO)3(bpy)]+ which finally yields pz-COOH and Re(CO)3(bpy)(CH3CN)+ as reaction products. This intermediate has been characterized by UV-vis and IR spectroscopies and by DFT calculations. The fully optimized DFT/CPCM structures for pz-CO2-Re(CO)3(bpy) and [pz-C(OH)O-Re(CO)3(bpy)]+ were compared with the X-ray structure of pz-CO2- Re(CO)3(bpy). The structural parameters associated to the carboxyl group in the protonated intermediate are between those of pz-CO2-Re(CO)3(bpy) and pz-COOH. Multivariate curve resolution methods were employed to obtain the spectrum of the protonated intermediate and the concentration profiles from the full matrix of timeresolved UV-vis spectra. The proposed mechanism was numerically simulated by using Runge-Kutta methods. Model parameters were estimated by non-linear regression fitting of the concentration profiles, yielding values of log(K) = 4.9 ± 0.3 and k = 0.16 ± 0.03 min-1 for the formation equilibrium constant and the decay rate constant of the protonated intermediate, respectively.
publishDate 2011
dc.date.none.fl_str_mv 2011-08
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/278677
Fagioli, Ulises; Garcia Einschlag, Fernando Sebastian; Cobos, Carlos Jorge; Ruiz, Gustavo Teodosio; Feliz, Mario Ruben; et al.; On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study; American Chemical Society; Journal of Physical Chemistry A; 115; 40; 8-2011; 10979-10987
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/278677
identifier_str_mv Fagioli, Ulises; Garcia Einschlag, Fernando Sebastian; Cobos, Carlos Jorge; Ruiz, Gustavo Teodosio; Feliz, Mario Ruben; et al.; On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study; American Chemical Society; Journal of Physical Chemistry A; 115; 40; 8-2011; 10979-10987
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/pdfplus/10.1021/jp206328q
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp206328q
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1854320989097164800
score 13.113929

Publicaciones similares